KR101380065B1 - Photocurable resin composition - Google Patents

Abstract

The photocurable resin composition is highly sensitive by including a photopolymerization initiator having two oxime ester groups in a molecule, a carboxyl group-containing resin, and a compound having two or more ethylenically unsaturated groups in the molecule, and excellent in the dryness of the dry coating film. In addition, it is possible to suppress generation of outgases during curing and to combine excellent positioning accuracy, high productivity, and reliability, for example, when forming a solder resist of a printed wiring board.

Description

[0001] PHOTOCURABLE RESIN COMPOSITION [0002]

TECHNICAL FIELD This invention relates to the photocurable resin composition used, for example as a soldering resist of a printed wiring board.

Conventionally, when patterning the soldering resist for printed wiring boards, the contact exposure system which makes a photomask contact is mainstream. However, in recent years, with high density of printed circuit boards, direct (straight drawing) exposure and split projection exposure that do not use a photomask have become widespread in view of excellent positioning accuracy.

Direct exposure is exposure while scanning directly with a laser beam or the like, and divisional projection exposure is to repeat exposure while aligning in a small exposure area using a projection exposure machine. Thus, since the soldering resist layer on a patterned wiring board is exposed or scanned repeatedly, there exists a problem that exposure takes very time with the conventional soldering resist whose appropriate exposure amount is 200 mJ / cm <2> or more.

Therefore, the soldering resist composition which can exhibit high photopolymerization capability is proposed. For example, in Patent Literature 1, acrylic acid is added to an epoxy group-containing polymer such as a copolymer of glycidyl methacrylate and methyl methacrylate, an acid anhydride is added, and 4-hydroxy is produced in the carboxyl group. Examples of photoresist inks in which butylglycidyl acrylate is reacted are illustrated. However, since the molecules of the side chain are very long and branched with respect to the main chain, there is a problem that the touch drying property of the dry coating film is very bad.

Moreover, in patent document 2, 3, the soldering resist composition which used the oxime ester initiator as a photoinitiator is disclosed. According to such a soldering resist composition, favorable touch drying property can be obtained. However, in exposure systems, such as direct exposure, super high sensitivity is calculated | required further because the sensitivity of a composition has a big influence on productivity. Moreover, there exists a problem that contamination arises by volatilizing the component of a photoinitiator as outgas.

For example, in the direct exposure or the split projection exposure in which the photomask is not in contact with the solder resist layer, the component of the photopolymerization initiator may volatilize as the outgas during exposure, resulting in contamination of the optical component in the exposure apparatus. In addition, in order to impart good solder heat resistance, after curing of the solder resist layer, post-curing is usually performed by thermosetting or UV exposure, and mounting is performed by reflow in a subsequent step. In that case, the component of a photoinitiator volatilizes as outgas, it is cooled, it solidifies, and it becomes a cause of contamination of a working environment.

Therefore, various methods for suppressing outgas are examined (for example, refer patent document 4). However, with higher density, higher performance, and the like of printed boards, it is required to further suppress contamination, and further suppression of outgas generation is required.

Japanese Patent Laid-Open No. 2004-264773 (claims) Japanese Patent Laid-Open No. 2007-286138 (claims) Japanese Patent Laid-Open No. 2007-286140 (patent claims) Japanese Patent No. 4008273

The present invention is highly sensitive, excellent in the dryness of the dry coating film, while suppressing the outgas generation during curing, for example, when forming a solder resist of a printed wiring board, excellent alignment accuracy and high productivity. And an object of the present invention is to provide a photocurable resin composition capable of having reliability.

According to one aspect of the present invention, there is provided a photocurable resin composition comprising a photopolymerization initiator having two oxime ester groups in a molecule, a carboxyl group-containing resin, and a compound having two or more ethylenically unsaturated groups in the molecule.

By this structure, it is highly sensitive, excellent in the touch-drying property of a dry coating film, suppresses generation | occurrence | production of the outgas at the time of hardening, and suppresses contamination when forming the soldering resist of a printed wiring board, and excellent position alignment. It is possible to combine precision, high productivity and reliability.

Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable that a photoinitiator has a carbazole structure. By having a carbazole structure, radicals are generated (photothermal heat) in the oxime ester group by light irradiation, and the molecular weight of the remaining carbazole dimer is large and volatilization is reduced, so that generation of outgas can be suppressed. .

Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable that a photoinitiator is an oxime ester compound represented by following General formula (I). By using such an oxime ester compound, volatilization is reduced more and it becomes possible to suppress the contamination by outgas.

(I)

(In formula, R <_1> is a hydrogen atom, a C1-C17 alkyl group, a C1-C8 alkoxy group, a phenyl group, a phenyl group (C1-C17 alkyl group, a C1-C8 alkoxy group, an amino group, C1-C8). Substituted by an alkylamino or dialkylamino group having an alkyl group of 1), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Substituted with an amino group), and R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms and carbon atoms). Substituted by an alkylamino group or dialkylamino group having 1 to 8 alkoxy groups, amino groups, alkyl groups having 1 to 8 carbon atoms, and naphthyl groups (alkyl groups having 1 to 17 carbon atoms, 1 carbon atom). And an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, n represents an integer from 0 to 1)

Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable to further contain a thermosetting resin. By containing a thermosetting component, heat resistance can be improved further.

Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable to contain a coloring agent further. By containing a coloring agent, it can use suitably as a soldering resist.

Moreover, the dry film can be obtained by apply | coating and drying the photocurable resin composition of one aspect of this invention on a film. A resist layer can be formed easily, without apply | coating a photocurable resin composition on a base material.

Moreover, even if it is low energy irradiation by apply | coating and drying the photocurable resin composition of 1 aspect of this invention to a base material, or laminating the dry film formed by apply | coating this on a film to a base material and photocuring by irradiation of an active energy ray, it is a favorable characteristic. Hardened | cured material which has a can be obtained. And it becomes possible to suppress the contamination by generation | occurrence | production of outgas at the time of hardening or in subsequent processes, such as reflow. Further, by applying direct exposure or the like, a printed wiring board having excellent alignment accuracy and high productivity can be provided.

The present invention is highly sensitive and excellent in the dryness of the dry coating film, while suppressing generation of outgases during curing and, for example, suppressing contamination when forming a solder resist of a printed wiring board, thereby providing excellent position. The photocurable resin composition which can have alignment precision, high productivity, and reliability can be provided.

Hereinafter, embodiments of the present invention will be described in detail.

The photocurable resin composition of this embodiment is characterized by including the photoinitiator which has two oxime ester groups in a molecule | numerator, a carboxyl group-containing resin, and the compound which has two or more ethylenically unsaturated groups in a molecule | numerator.

By using the photoinitiator which has two oxime ester groups in a molecule | numerator, a highly sensitive photocurable resin composition can be obtained. Moreover, when hardening this, it becomes possible to suppress generation | occurrence | production of outgas in further processes (heating process), such as reflow.

As mentioned above, although generation | occurrence | production of outgas is suppressed to some extent in one oxime ester in 1 molecule, according to the photoinitiator in this embodiment, it becomes possible to suppress outgas generation further. Since the photoinitiator in this embodiment is very sensitive, even when the addition amount is small, the equivalent or more sensitivity is obtained, and when it reacts with ethylenically unsaturated double bond by having two oxime ester groups in a molecule | numerator, It is considered that it is because it is blown into a network as a bridge | crosslinking point.

That is, it functions as a photoinitiation crosslinking type photoinitiator which reacts as a bifunctional functional group between the molecule | numerators of carboxyl group-containing resin which has ethylenically unsaturated group, or the compound which has ethylenically unsaturated group.

Specifically, the oxime ester compound which has a carbazole structure represented by following formula (I) is mentioned.

(I)

(In formula, R <_1> is a hydrogen atom, a C1-C17 alkyl group, a C1-C8 alkoxy group, a phenyl group, a phenyl group (C1-C17 alkyl group, a C1-C8 alkoxy group, an amino group, C1-C8). Substituted by an alkylamino or dialkylamino group having an alkyl group of 1), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Substituted with an amino group), and R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms and carbon atoms). Substituted by an alkylamino group or dialkylamino group having 1 to 8 alkoxy groups, amino groups, alkyl groups having 1 to 8 carbon atoms, and naphthyl groups (alkyl groups having 1 to 17 carbon atoms, 1 carbon atom). And an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, n represents an integer from 0 to 1)

By using such an oxime ester compound, volatilization is further reduced and it becomes possible to suppress the contamination by outgas. This is considered to be because the radical generation (photothermal heat) point by light irradiation is an oxime ester group, and the remaining carbazole dimer is a compound with a large molecular weight compared with the conventional photoinitiator.

In formula (I), R ₁ and R ₂ are each a methyl group or an ethyl group, R ₃ is methyl or phenyl, Ar is a bond, phenylene, naphthylene or thienylene, and n is preferably 0.

As a compounding quantity of such a photoinitiator, it is preferable that it is 0.01-5 weight part with respect to 100 weight part of carboxyl group-containing resin, and when it is more than 5 weight part, light absorption will increase, the photoreactivity of a resist bottom part will fall, an undercut will occur, and a touch key will dry. The composition worsens. On the other hand, when it is less than 0.01 weight part, the photocurability on copper will be inadequate, peeling a coating film and coating film characteristics, such as chemical-resistance, will fall. More preferably, it is 0.1-3 weight part.

The carboxyl group-containing resin in the photocurable resin composition of this embodiment is used in order to provide alkali developability, and well-known resin which contains a carboxyl group in a molecule | numerator can be used. In particular, in view of photocurability and developability, a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferable. The unsaturated double bond is more preferably derived from acrylic acid or methacrylic acid, or derivatives thereof. Specific examples are shown below.

(1) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(2) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate, a dialcohol compound containing a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid, and a polycarbonate polyol, a polyether polyol Containing urethane resin obtained by a mid-portion reaction of a diol compound such as a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(3) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A terminal carboxyl group-containing urethane resin formed by making an acid anhydride react with the terminal of the urethane resin by polyaddition reaction of diol compounds, such as A type alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group, and alcoholic hydroxyl group.

(4) bifunctional epoxy resins such as diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin The carboxyl group-containing photosensitive urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified | denatured product, a carboxyl group-containing dialcohol compound, and a diol compound.

(5) During the synthesis of the resin of (2) or (4) described above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (meth ) Acrylicated carboxyl group-containing urethane resin.

(6) Having one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate during synthesis of the resin of (2) or (4) above The carboxyl group-containing urethane resin which added the compound and was terminal (meth) acrylated.

(7) (meth) acrylic acid is made to react with the bifunctional or more than one polyfunctional (solid) epoxy resin mentioned later, and dibasic acid anhydrides, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, to the hydroxyl group which exists in a side chain. Carboxyl group containing photosensitive resin which added this.

(8) A carboxyl group in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin further epoxidized with epichlorohydrin, to which a hydroxyl group of a bifunctional (solid) epoxy resin described later is added, and a dibasic anhydride is added to the resulting hydroxyl group. Containing photosensitive resin.

(9) Cyclic carbonates, such as cyclic ethers, such as ethylene oxide, and a propylene carbonate, are added to polyfunctional phenol compounds, such as novolak, and the obtained hydroxyl group is partially esterified by (meth) acrylic acid, and a polybasic acid anhydride is made to the remaining hydroxyl group. The carboxyl group-containing photosensitive resin made to react.

(10) To these resins (1) to (9), one epoxy group and one or more (meth) groups in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, etc. Carboxyl group-containing photosensitive resin formed by adding the compound which has a) acryloyl group.

Such carboxyl group-containing resin can be used not only in these, but can also be used 1 type or in mixture of multiple types.

In addition, (meth) acrylate is a term used here generically for an acrylate, a methacrylate, and a mixture thereof, The same also about the expression of another similarity hereafter.

Since such carboxyl group-containing resin has many glass carboxyl groups in the side chain of a backbone polymer, image development by a rare alkali aqueous solution is attained.

In addition, the acid value of such carboxyl group-containing resin is 40-200 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary, and in some cases, the furnace It dissolves and peels with a developing solution without distinguishing a light part and an unexposed part, and drawing of a normal resist pattern becomes difficult. And more preferably 45 to 120 mgKOH / g.

Moreover, although the weight average molecular weight of such carboxyl group-containing resin changes with resin skeleton, it is preferable that it is generally 2,000-150,000. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coating film after exposure is bad, a film reduction may occur at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and there exists a tendency for storage stability to deteriorate. More preferably from 5,000 to 100,000.

As for the compounding quantity of such carboxyl group-containing resin, 20-80 mass% is suitable in a photocurable resin composition. If it is less than 20 mass%, film strength will fall. On the other hand, when more than 60 mass%, the viscosity of a composition becomes high and applicability | paintability etc. fall. And more preferably 30 to 60 mass%.

In the photocurable resin composition of this embodiment, the compound which has 2 or more ethylenically unsaturated groups in a molecule | numerator is photocured by active energy ray irradiation, and insolubilizes carboxyl group-containing resin in aqueous alkali solution, or helps insolubilization. It is used for

As such a compound, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Polyhydric acrylates, such as ethylene oxide adduct or propylene oxide adduct of phenoxy acrylate, bisphenol A diacrylate, and these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; And urethane acrylate, melamine acrylate, and / or respective methacrylates corresponding to these acrylates.

Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolak type epoxy resin with acrylic acid, or an epoxy acrylate resin obtained by reacting a hydroxy acrylate such as pentaerythritol triacrylate with an isophorone di And an epoxy urethane acrylate compound obtained by reacting a half urethane compound of a diisocyanate such as isocyanate. Such an epoxy acrylate resin can improve photo-curability without lowering the touch-dry composition.

It is preferable that the compounding quantity of such a compound is 5-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When less than 5 mass parts, photocurability falls and pattern formation becomes difficult by alkali image development after active energy ray irradiation. On the other hand, if it exceeds 100 parts by mass, the solubility in an aqueous alkali solution is lowered and the coating film becomes weak. More preferably 1 to 70 parts by mass.

In the photocurable resin composition of this embodiment, photoinitiators other than the photoinitiator which has two oxime ester groups in the molecule mentioned above can also be used.

For example, one or more photoinitiators selected from the group consisting of an oxime ester photoinitiator having one oxime ester group in one molecule, an α-aminoacetophenone photoinitiator and an acylphosphine oxide photoinitiator can be used. .

Examples of the oxime ester photopolymerization initiator include CGI-325 manufactured by BASF Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, and N-1919 manufactured by Adeka Co., Ltd. have. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

It is preferable that the compounding quantity of such an oxime ester type photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing resin. If it is less than 0.01 mass part, the photocurability on copper will run out, peeling a coating film and coating film characteristics, such as chemical-resistance, will fall. On the other hand, when it exceeds 5 mass parts, the effect of reducing outgas will not be acquired, and the light absorption on the surface of a soldering resist coating will become deep, and there exists a tendency for deep-curing property to fall. More preferably, it is 0.5-3 mass parts.

Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, N, N-dimethylaminoacetophenone, and the like. Examples of commercially available products include Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by BASF Japan.

As an acyl phosphine oxide type photoinitiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6- trimethyl benzoyl)-phenyl phosphine oxide, bis (2, 6- dime specifically, Oxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Lucirin TPO manufactured by BASF Corporation, Irgacure 819 manufactured by BASF Japan Corporation.

It is preferable that the compounding quantity of these (alpha)-amino acetophenone type photoinitiators and an acyl phosphine oxide type photoinitiators is 0.01-15 mass parts with respect to 100 mass parts of carboxyl group-containing resin. If it is less than 0.01 mass part, similarly, the photocurability on copper will be inferior, the coating film will peel, and coating film characteristics, such as chemical-resistance, will fall. On the other hand, when it exceeds 15 mass parts, the effect of reducing outgas will not be acquired, and the light absorption on the surface of a soldering resist coating will become deep, and there exists a tendency for deep-curing property to fall. More preferably 0.5 to 10 parts by mass.

In addition, as a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for the photocurable resin composition of this embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, Tertiary amine compounds, xanthone compounds and the like.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. .

Specific examples of the anthraquinone compound include 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and the like. .

Specific examples of the ketal compound include acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- Benzoyl-4'-propyldiphenyl sulfide and the like.

Specifically as a tertiary amine compound, For example, an ethanolamine compound and the compound which has a dialkylaminobenzene structure, For example, as a commercial item 4,4'- dimethylamino benzophenone (Nissocure (made by Nippon Soda Co., Ltd.) Dialkylaminobenzophenone, 7- (diethylamino) -4-methyl-2H-1-benzopyran, such as MABP) and 4,4'-diethylaminobenzophenone (EAB by Hodogaya Chemical Co., Ltd.). Dialkylamino group-containing coumarin compounds such as 2-one (7- (diethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Gayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), 2- Ethyl dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics Co., Ltd.), p-dimethyl Aminobenzoic acid isoamyl ethyl ester (Gayacure DMBI by Nippon Kayaku Co., Ltd.), 4-di 2-ethylhexyl (Esolol 507 by Van Dyk), 4,4'- diethylamino benzophenone (EAB by Hodogaya Chemical Co., Ltd.) etc. are mentioned. .

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, it is preferable to contain a thioxanthone compound from the point of deep-hardening property. Especially, it is preferable to contain thioxanthone compounds, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone. Do.

As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin. When the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product. More preferably 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, Particularly preferred.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is also preferable because of its low toxicity. Since the dialkylamino group-containing coumarin compound is in the ultraviolet region with a maximum absorption wavelength of 350 to 410 nm, the coloring solder resist reflects the color of the colored pigment itself using a color pigment, as well as a colorless and transparent photosensitive composition. It is possible to provide a membrane. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it shows the excellent sensitizing effect with respect to the laser beam of wavelength 400-410 nm.

As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When the compounding quantity of a tertiary amine compound is less than 0.1 mass part, there exists a tendency for sufficient sensitization effect not to be acquired. If the amount is more than 20 parts by mass, the light absorption at the surface of the dried solder resist coating film by the tertiary amine compound becomes severe, and the deep portion curing property tends to be lowered. More preferably 0.1 to 10 parts by mass.

These photoinitiators, photoinitiation aids, and sensitizers can be used alone or as a mixture of two or more thereof.

It is preferable that the total amount of such a photoinitiator, a photoinitiator, and a sensitizer is 35 mass parts or less with respect to 100 mass parts of said carboxylic acid containing resins. When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

Moreover, since these photoinitiators, a photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may function as a ultraviolet absorber. However, they are not used for the purpose of improving the sensitivity of the composition. By absorbing light of a specific wavelength as needed, it improves the light reactivity of the surface, and changes the line shape and opening of the resist into vertical, tapered and inverse tapered shapes, and improves the processing accuracy of the line width and the opening diameter. Can be.

In order to improve a sensitivity, the photocurable resin composition of this embodiment can use N phenylglycine, phenoxy acetic acid, thiophenoxy acetic acid, mercaptothiazole, etc. which are well-known as a chain transfer agent.

Specifically, For example, Chain transfer agent which has carboxyl groups, such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and its derivative (s); Chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropane diol, mercaptobutanediol, hydroxybenzene thiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

Moreover, a polyfunctional mercaptan type compound can be used, Specifically, such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethyl sulfide, etc. Aromatic thiols such as aliphatic thiols, xylylenedimercaptan, 4,4'-dimercaptodiphenylsulfide, and 1,4-benzenedithiol; (Mercaptoacetate), ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris Poly (mercaptoacetates) of polyhydric alcohols such as mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexakis (mercaptoacetate); (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate) , Trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis - mercapto propionate); poly (3-mercaptopropionates) of polyhydric alcohols; 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 3H, 5H) -triene, and poly (mercaptobutyrates) such as pentaerythritol tetrakis (3-mercaptobutyrate).

Moreover, the heterocyclic compound which has a mercapto group can be used, For example, mercapto-4-butyrolactone (alias 2-mercapto-4-butanolide), 2-mercapto-4- Methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylothiolactone, 2-mercapto-4-butyrolactam, N-methoxy 2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mer Capto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valero Lactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam and 2-mercapto-6 -Hexanolactam, etc. are mentioned.

Heterocyclic compounds having these mercapto groups are preferable since they do not impair developability of the photocurable resin composition, and specifically, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, Preference is given to 2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole.

These chain transfer agents may be used alone or in combination of two or more.

It is preferable that the total amount of such chain transfer agents becomes a range which will be 5 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin. If it exceeds 5 parts by mass, not only the sensitivity will be improved by addition of more than necessary, but also these and ethylenically unsaturated groups will react, and developability tends to decrease.

A thermosetting resin can be added to the photocurable resin composition of this embodiment in order to provide heat resistance. Specifically, for example, two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule such as a polyfunctional epoxy compound, a polyfunctional oxetane compound, and an episulfide resin , Amine resins such as polyisocyanate compounds, blocked isocyanate compounds, compounds having two or more isocyanate groups or blocked isocyanate groups, melamine resins, benzoguanamine resins, derivatives thereof, bismaleimide, oxazine, cyclocarbonate compounds, etc. And well-known thermosetting resins, such as carbodiimide resin, are mentioned.

Especially preferred is a thermosetting resin having two or more cyclic (thio) ether groups in the molecule. A thermosetting resin having two or more cyclic (thio) ether groups in such a molecule is a compound having at least two or three or more of three, four or five membered cyclic ether groups, or cyclic thioether groups in the molecule. For example, a compound having at least two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound, a compound having at least two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound, a compound having two or more episulfide groups in a molecule, That is, episulfide resin etc. are mentioned.

As a polyfunctional epoxy compound, specifically, as a commercial item, jER (trademark) 828, jER834, jER1001, jER1004 by Mitsubishi Chemical Corporation, Epiclone (trademark) 840, Epiclone 850, and Epi make Clone 1050, Epiclone 2055, Eptoto (registered trademark) YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER made by Epoxy Seiko Co., Ltd. 661, DER664, Araldite 6071 made by Huntsman Advanced Materials, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo (registered trademark) ESA-011 made by Sumitomo Kagaku Kogyo Co., Ltd. Bisphenol A type epoxy resins such as AER330, AER331, AER661, and AER664 manufactured by ESA-014, ELA-115, ELA-128, and Asahi Kasei Kogyo Co., Ltd .; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152 manufactured by DIC Corporation, Epiclone 165, Efototo YDB-400, YDB-500 manufactured by Shinnika Epoxy Seizou Corporation, DER542 manufactured by Dow Chemical, BASF Japan Brominated epoxy resins such as Araldite 8011, Sumitomo Chemical Co., Ltd., Sumerepoxy ESB-400, ESB-700, and Asahi Kasei Kogyo AER711, AER714; Mitsubishi Chemical Corporation jER152, jER154, Dow Chemical Co., Ltd. DEN431, DEN438, DIC Co., Ltd. Epiclone N-730, Epiclone N-770, Epiclone N-865, Shin-Nika Epoxy Seizo Co., Ltd. Efototo YDCN-701, YDCN-704, Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 by BASF Japan, EPPN (registered trademark) -201, manufactured by Nippon Kayaku Co., Ltd. EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumiepoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN-299, etc. Novolac type epoxy resins; Epiclon 830, manufactured by DIC Corporation, jER807, manufactured by Mitsubishi Chemical Corporation, Efototo YDF-170, YDF-175, YDF-2004, manufactured by BASF Japan, and Araldite XPY306, manufactured by BASF Japan. Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resins such as Efototo ST-2004, ST-2007, ST-3000 manufactured by Shinnika Epoxy Seijo Corporation; Glycidyl such as jER604 manufactured by Mitsubishi Chemical Corporation, Efototo YH-434 manufactured by Shintika Epoxy Seizo Corporation, Araldite MY720 manufactured by BASF Japan, Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Amine type epoxy resins; Hydantoin type epoxy resins, such as Araldite CY-350 by BASF Japan company; Alicyclic epoxy resins such as Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 manufactured by BASF Japan, and CY179; Trihydroxyphenyl methane type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501 and EPPN-502 manufactured by Dow Chemical Corporation; Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, YL-6121 manufactured by Mitsubishi Chemical Corporation, or mixtures thereof; Bisphenol S type epoxy resins, such as EBPS-200 by Nippon Kayaku Co., Ltd., EPX-30 by Adeka Co., and EXA-1514 by DIC Co., Ltd .; Bisphenol A novolak-type epoxy resins, such as the jER157S by Mitsubishi Chemical Corporation; Tetraphenylolethane type epoxy resins such as jERYL-931 manufactured by Mitsubishi Chemical Corporation and Araldite 163 manufactured by BASF Japan; Heterocyclic epoxy resins such as Araldite PT810 manufactured by BASF Japan, TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd .; Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT manufactured by Nichi Oil Company; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Shinnika Epoxy Seijo Co .; ESN-190, ESN-360 manufactured by Shinnittsu Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nichi Oil Company; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives, such as Daicel Chemical Industries, Ltd. PB-3600, CTBN modified epoxy resins, such as YR-102 and YR-450, manufactured by Shin-Naka Epoxy Seizo Co., etc. are mentioned.

These polyfunctional epoxy compounds can be used individually or in combination of 2 or more types. Of these, novolak type epoxy resins, heterocyclic epoxy resins, bisphenol A type epoxy resins, and mixtures thereof are particularly preferable.

Specific examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1 , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohols, novolak resins, poly (p-hydroxystyrene), cardo bisphenols, calix arenes and calyx rezos The etherified substance with resin which has hydroxyl groups, such as a leucine arene or silsesquioxane, etc. are mentioned. Other examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Specific examples of the episulfide resin include bisphenol A episulfide resins such as YL7000 manufactured by Mitsubishi Chemical Corporation. An episulfide resin in which an oxygen atom of the epoxy group of the novolac epoxy resin is replaced with a sulfur atom using the same synthetic method can also be used.

It is preferable that the compounding quantity of the thermosetting resin which has two or more cyclic (thio) ether group in such a molecule | numerator is 0.6-2.5 equivalent with respect to 1 equivalent of carboxyl group of carboxyl group-containing resin. When less than 0.6 equivalent, a carboxyl group remains in a soldering resist film, and heat resistance, alkali resistance, electrical insulation, etc. fall. On the other hand, when it exceeds 2.5 equivalents, the strength and the like of the coating film deteriorate because a low molecular weight cyclic (thio) ether group remains in the dried coating film. More preferably 0.8 to 2.0 equivalents.

As a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having two or more blocked isocyanate groups in one molecule, that is, a blocked isocyanate group Compounds and the like.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.

Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate and o-chloro Silylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer are mentioned.

Specific examples of the aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. have.

Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate.

As a block isocyanate compound which has two or more blocked isocyanate groups in 1 molecule, the addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. The blocked isocyanate group contained in the block isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is temporarily inactivated. When the blocked isocyanate group is heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

Isocyanurate type, a biuret type, an adduct type etc. are mentioned as an isocyanate compound which can react with an isocyanate blocking agent. For example, aromatic polyisocyanates, aliphatic polyisocyanates or alicyclic polyisocyanates are used.

Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate and o-chloro Silylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer are mentioned.

Specific examples of the aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. have.

Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate.

As an isocyanate blocking agent, For example, Phenol blocking agents, such as a phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; Methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycol Alcohol blocking agents such as butyl acid, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scavengers, acetal aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide block agents such as acetic amide and benzamide; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

A block isocyanate compound may be commercially available, for example, Sumidur (R) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (TM) TPLS by Sumitomo Bayer Urethane Co., Ltd. -2957, TPLS-2062, TPLS-2078, TPLS-2117, Des Motem (DESMOTHERM; 2170), Des Motem 2265, Nippon Polyurethane Co., Ltd. Coronate 2512, Coronate 2513, Coronate 2520 , B-830, B-815, B-846, B-870, B-874, B-882, TPA-B80E, 17B-60PX, E402-B80T manufactured by Asahi Kasei Chemicals, Inc. Can be mentioned. Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The compound which has two or more isocyanate groups or blocked isocyanate groups in these 1 molecule can be used individually by 1 type or in combination of 2 or more types.

It is preferable that the compounding quantity of the compound which has two or more isocyanate groups or blocked isocyanate groups in such 1 molecule is 1-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When it is less than 1 mass part, sufficient toughness of a coating film is not obtained, and when it exceeds 100 mass parts, storage stability falls. More preferably 2 to 70 parts by mass.

Moreover, amine resins, such as melamine resin and benzoguanamine resin, its derivative (s) etc. are mentioned as a thermosetting resin. Specifically, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned, for example.

Moreover, the alkoxy methylation melamine compound, the alkoxy methylation benzoguanamine compound, the alkoxy methylation glycoluril compound, and the alkoxy methylation element compound which are obtained by converting these methylol groups by the alkoxy methyl group can be used. At this time, it does not specifically limit about the kind of alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. In particular, it is preferable that the concentration of formalin that is human or environmentally friendly is 0.2% or less.

As these commercial items, Cymel (registered trademark) 300, copper 301, copper 303, copper 370, copper 325, copper 327, copper 701, copper 266, copper 267, copper manufactured by Mitsui Cyanamide, for example. 238, copper 1141, copper 272, copper 202, copper 1156, copper 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300, Nikalak (registered trademark) Mx-750, copper Mx- 032, Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw- 30HM, copper Mw-390, copper Mw-100LM, copper Mw-750LM, etc. are mentioned.

These thermosetting resins can be used individually or in combination of 2 or more types.

It is preferable that the compounding quantity of such an amine resin and its derivatives is 1-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When it is less than 1 mass part, sufficient toughness of a coating film is not obtained, and when it exceeds 100 mass parts, storage stability falls. More preferably 2 to 70 parts by mass.

When using the thermosetting resin which has a 2 or more cyclic (thio) ether group in a molecule | numerator, it is preferable to contain a thermosetting catalyst. Specific examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 Imidazole derivatives such as -phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine.

As commercially available products, specifically, for example, an imidazole compound, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ manufactured by Shikoku Kasei Kogyo Co., Ltd. Trademark) 3503N, U-CAT3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof) and the like. In particular, it is not limited to these, What is necessary is just the thermosetting catalyst of an epoxy resin or an oxetane compound, or the thermosetting catalyst which promotes reaction of an epoxy group and / or an oxetanyl group, and a carboxyl group, and can use together single or 2 types or more. have.

In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine and 2-vinyl-2,4-, which also function as an adhesion imparting agent Diamino-S-triazine, 2-vinyl-4, 6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-tri S-triazine derivatives, such as an azine and isocyanuric acid adduct, can also be used. It is more preferable to use these together with a thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantitative ratio, For example, 0.1-20 mass parts with respect to 100 mass parts of thermosetting resins which have two or more cyclic (thio) ether groups in a carboxyl group-containing resin or molecule | numerator, More preferably, it is 0.5-15.0 mass parts.

An adhesion promoter can be used for the photocurable resin composition of this embodiment in order to improve adhesiveness between layers or adhesiveness of the photosensitive resin layer and a base material. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1, for example -Phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotria Sol, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

In addition, a binder polymer can be used for the photocurable resin composition of this embodiment for the purpose of improving a touch-drying property, an improvement of handleability, etc. Examples of the binder polymer include polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyesteramide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, and phenoxy clock polymers. Can be. These binder polymers can be used alone or as a mixture of two or more thereof.

In addition, the photocurable resin composition of this embodiment can use an elastomer for the purpose of providing flexibility, improving the fragility of hardened | cured material, etc. Examples of the elastomer include a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer and an olefin elastomer. Moreover, the elastomer etc. which modified | denatured some or all the epoxy groups of the epoxy resin which has various skeletons with both terminal carboxylic acid modified butadiene- acrylonitrile rubber can also be used. The epoxy-containing polybutadiene elastomer, the acrylic-containing polybutadiene elastomer, the hydroxyl group-containing polybutadiene elastomer, and the hydroxyl group-containing isoprene elastomer may also be used. These elastomers can be used alone or as a mixture of two or more thereof.

In addition, the photocurable resin composition of this embodiment can mix | blend a coloring agent. As a coloring agent, well-known coloring agents, such as blue, green, yellow, and red, can be used, and any of a pigment, dye, and a pigment may be used. However, it is preferable not to contain a halogen from a viewpoint of environmental load reduction and an influence on a human body. Specifically, the following color index (C.I .; issued by The Society of Dyers and Colorists) numbers is attached.

Phthalocyanine series, anthraquinone series, etc. are used as a blue coloring agent. As a pigment system, for example, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, pigment blue 60 is mentioned.

As the dye system, for example, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67 , Solvent blue 70, and the like. In addition to these, metal substituted or unsubstituted phthalocyanine compounds may also be used.

As the green colorant, phthalocyanine series, anthraquinone series, perylene series and the like are used. For example, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, solvent green 28, etc. are mentioned. In addition to these, metal substituted or unsubstituted phthalocyanine compounds may also be used.

As the yellow colorant, monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like are used. Specifically, the following are mentioned.

Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183

Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198

Condensation Azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 18

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185

Anthraquinone series: solvent yellow 163, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202

As a red coloring agent, a monoazo system, a disazo system, a monoazo lake system, a benzimidazolone system, a perylene system, a diketopyrrolopyrrole system, a condensation azo system, an anthraquinone system, a quinacridone system, etc. can be used. Specifically, the following are mentioned.

Monoazo series: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269

Disazo system: Pigment Red 37, 38, 41

48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224

Diketopyrrolopyrrole system: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272

Condensation azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207

Quinacridone system: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209

In addition, coloring agents such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone.

Specifically, for example, pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36 as a purple colorant, pigment orange 5, pigment orange 13, pigment orange 14 as an orange colorant. , Pigment Orange 16, Pigment Orange 17, Pigment Orange 24, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 40, Pigment Orange 43, Pigment Orange 46, Pigment Orange 49 Pigment Orange 51, Pigment Orange 61, Pigment Orange 63, Pigment Orange 64, Pigment Orange 71, Pigment Orange 73, Pigment Brown 23, Pigment Brown 25, Brown Black as Pigment Black 1, pigment black 7, etc. are mentioned.

Although the compounding ratio of such a coloring agent does not have a restriction | limiting in particular, It is preferable that it is 0-10 mass parts with respect to 100 mass parts of carboxyl group-containing resin in order to obtain desired coloring, without affecting a characteristic. More preferably, it is 0.1-5 mass parts.

In order to prevent oxidation, you may add antioxidant to the photocurable resin composition of this embodiment. Most of the polymer materials are oxidatively deteriorated in sequence once oxidation starts, resulting in deterioration of the function of the polymer material, decomposing the radical scavenger that invalidates the generated radicals, and decomposing the generated peroxide into a harmless substance. Antioxidants, such as a peroxide decomposer which prevents a radical from generating, are effective.

Specifically as antioxidant which functions as a radical trapping agent, hydroquinone, 4-tert- butylcatechol, 2-t- butyl hydroquinone, hydroquinone monomethyl ether, 2, 6- di-t- butyl- p- Cresol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'di-t- Phenolic compounds, such as butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds, such as metaquinone and benzoquinone, bis (2,2) And amine compounds such as 6,6-tetramethyl-4-piperidyl) -sebacate and phenothiazine.

A radical scavenger may be commercially available, and specifically, it can be used for example, adecas tab (trademark) AO-30 by Adeka Corporation, adecas tab AO-330, adecas tab AO-20, adecas tab LA -77, adecastab LA-57, adecastab LA-67, adecastab LA-68, adecastab LA-87, Irganox (IRGANOX (registered trademark) 1010, Irganox made by BASF Japan) 1035, Irganox 1076, Irganox 1135, TINUVIN® 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 and the like.

Specifically as antioxidant which functions as a peroxide decomposer, For example, phosphorus compounds, such as a triphenyl phosphite, pentaerythritol tetralauryl thio propionate, the dilauryl thiodipropionate, distearyl 3,3 Sulfur type compounds, such as "-thiodipropionate, etc. are mentioned.

The peroxide decomposer may be commercially available, and specifically, for example, Adecas tab TPP manufactured by Adeka Co., Mark AO-412S by Adeka Agus Chemical Co., Ltd., and a smistizer manufactured by Sumitomo Chemical Co., Ltd. ) TPS, etc. are mentioned.

These antioxidants can be used alone or in combination of two or more.

Moreover, in the photocurable resin composition of this embodiment, a ultraviolet absorber can also be added further. Since the polymer material absorbs light and causes decomposition and deterioration, a stabilization measure against ultraviolet rays is effective.

As a ultraviolet absorber, a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an anthranilate derivative, a dibenzoyl methane derivative, a coumarin derivative, etc. are mentioned, for example.

Specific examples of the benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2 2, 4- dihydroxy-4- methoxy benzophenone, 2, 4- dihydroxy benzophenone, etc. are mentioned.

Specific examples of the benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di -tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like.

Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole. , 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl Phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) Benzotriazole is mentioned.

Specific examples of the triazine derivatives include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine, and the like.

As such a ultraviolet absorber, what is marketed may be sufficient, Specifically, For example, Tinuvin PS, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928 by BASF Japan Co., Ltd., Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, etc. are mentioned.

These ultraviolet absorbers can be used individually or in combination of 2 or more types, and can stabilize stabilization of the hardened | cured material obtained from the photocurable resin composition of this embodiment by using together with antioxidant.

The photocurable resin composition of this embodiment can mix | blend a filler as needed. As such a filler, a known inorganic or organic filler can be used.

In order to raise the physical strength of a coating film, etc., especially barium sulfate, spherical silica, and talc are used preferably.

Moreover, in order to acquire a white appearance and flame retardance, metal hydroxides, such as a titanium oxide, a metal oxide, and aluminum hydroxide, can be used as a extender pigment filler.

It is preferable that the compounding quantity of such a filler is 75 mass% or less of the whole composition. When the blending amount of the filler exceeds 75 mass% of the total amount of the composition, the viscosity of the insulating composition becomes high, and the coating and the formability are lowered, and the cured product becomes fragile. And more preferably 0.1 to 60 mass%.

The photocurable resin composition of this embodiment can also add thixotropic agents, such as fine-grained silica, organic bentonite, montmorillonite, hydrotalcite, etc. as needed. The aging stability as a thixotropic agent is preferably organic bentonite or hydrotalcite, and particularly hydrotalcite has excellent electrical properties.

Moreover, well-known additives, such as a thermal polymerization inhibitor, antifoamers and / or leveling agents, such as a silicone type, a fluorine type, a polymeric type, a silane coupling agent, such as an imidazole type, a thiazole type, a triazole type, and a rust inhibitor, can be mix | blended.

Moreover, the organic solvent can be used for the photocurable resin composition of this embodiment for the synthesis | combination of carboxyl group-containing resin, manufacture of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. Specifically, For example, ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents are used alone or as a mixture of two or more kinds.

The photocurable resin composition of the present embodiment may further contain known thermal polymerization inhibitors, finely divided silicas, thickeners such as organic bentonite and montmorillonite, antifoaming agents such as silicones, fluorine and polymers, leveling agents, imidazoles, and thiazoles. Additives, such as a silane coupling agent and a rust inhibitor, such as a triazole type, can be mix | blended.

Among these, a thermal polymerization inhibitor can be used in order to prevent thermal superposition | polymerization or superposition | polymerization superposition | polymerization of a polymeric compound. Specific examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydride. Roxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl- 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al And chelate with.

The photocurable resin composition of this embodiment is manufactured by predetermined | prescribed compounding ratio, for example, it adjusts to the viscosity suitable for an application | coating method with the organic solvent, and then immersion coating method, flow coating method, roll coating method, bar coater method, It is apply | coated on a base material by methods, such as a screen printing method and a curtain coating method.

As a base material, in addition to the printed wiring board and flexible printed wiring board which were formed beforehand, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper-epoxy resin, Copper clad laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafer boards of all grades (FR-4, etc.) using composite materials such as synthetic fibers-epoxy resins, fluororesins, polyethylene, PPO, and cyanate esters Can be used.

And the tack free dry coating film is formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC.

At this time, the volatilization drying is a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like, which has a heat source such as a hot air heating system by steam, and makes a countercurrent contact with the hot air in the dryer and from the nozzle to the support. It can carry out using the method of spraying.

Thereafter, active energy rays are selectively irradiated onto the coating film by direct exposure, divided projection exposure, or the like to photocure the exposed portion.

At this time, as an exposure machine used for active energy ray irradiation, a UV device such as a direct drawing device (for example, a laser direct imaging device for drawing an image with a laser directly by CAD data from a computer) and an ultra-high pressure mercury lamp are used. You can use a drawing device directly. As such a direct drawing apparatus, things, such as the Nippon Orbotech company make and the Pantax company make, can be used, for example. In addition, an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (ultra) high pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, and the like can be used.

As an active energy ray, peak wavelength should just be the range of 300-450 nm in which the photocurable resin composition of this embodiment has sufficient light absorption ability. In the case of using a laser, a medium such as a gas laser or a solid laser is not particularly limited as long as it emits laser light having a wavelength in this range.

Moreover, although the exposure amount changes with film thickness etc., in general, in the photocurable resin composition of 5-200 mJ / cm <2> and this embodiment, since especially high sensitivity is obtained, Preferably it is 5-100 mJ / cm <2>, More Preferably it can be in the range of 5-50 mJ / cm <2>.

Then, the unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern. As a developing method, the dipping method, the shower method, the spray method, the brush method, etc. can be used. As a developing solution, aqueous alkali solution, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, can be used. Specifically, 0.3-3 weight% sodium carbonate aqueous solution can be used, for example.

In addition, it is preferable to heat to a temperature of, for example, about 140 to 180 ℃ to thermoset. By thermosetting, the carboxyl group of the carboxyl group-containing resin and a thermosetting component such as a thermosetting resin having two or more cyclic ether groups and / or cyclic thioether groups react with each other, and thus heat resistance, chemical resistance, hygroscopicity, adhesion, and electrical properties. Etc., it becomes possible to improve.

In addition, the photocurable resin composition of this embodiment is not apply | coated directly on a base material as mentioned above, For example, it coats previously on a film, and winds up the dried coating film dried as a film, and bonds on a base material as a dry film You can also

A dry film has a structure which the carrier film, the soldering resist layer (photocurable resin composition layer), and the peelable cover film used as needed are laminated | stacked in this order, for example. After forming a soldering resist layer on a carrier film, a cover film is laminated | stacked on it as needed, or after forming a soldering resist layer on a cover film, a dry film is obtained by laminating | stacking this laminated body to a carrier film.

At this time, as a carrier film, thermoplastic films, such as polyethylene terephthalate and a polyester film, whose thickness is 2-150 micrometers are used.

In addition, the solder resist layer is formed by uniformly applying a photocurable resin composition to a carrier film or a cover film with a blade coater, a lip coater, a coater coater, a film coater, etc. in a thickness of 10 to 150 ㎛, and dried.

And although a polyethylene film, a polypropylene film, etc. can be used as a cover film, it is good that adhesive force with a soldering resist layer is smaller than a carrier film.

Using such a dry film, a protective film (permanent protective film) can be produced on a printed wiring board as follows, for example. First, a cover film is peeled off as needed, a soldering resist layer and a printed circuit board overlap, and a soldering resist layer is formed on a printed wiring board by bonding together using a laminator or the like. And a protective film (permanent protective film) is formed by performing exposure, image development, and heat-hardening with respect to a soldering resist layer. In addition, what is necessary is just to peel a carrier film before exposure or after exposure.

Hereinafter, although an Example and a comparative example demonstrate this embodiment concretely, it cannot be overemphasized that this invention is not limited to these Examples. In addition, below, "part" and "%" are all mass references | standards unless there is particular notice.

(Synthesis Example 1)

In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts of dipropylene glycol monomethyl ether as a solvent was heated to 110 ° C, 174.0 parts of methacrylic acid and ε-caprolactone modified methacrylic acid (average molecular weight 314) 174.0 A mixture of 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether, and 12.0 parts of t-butylperoxy 2-ethylhexanoate (Perbutyl® O manufactured by Nichi Corporation) as a polymerization catalyst, It dripped over 3 hours, and also stirred at 110 degreeC for 3 hours, deactivated the polymerization catalyst, and obtained the resin solution.

After cooling this resin solution, 289.0 parts of cyclocel-A200 manufactured by Daicel Chemical Industries, Ltd., 3.0 parts of triphenylphosphine, and 1.3 parts of hydroquinone monomethyl ether were added, and the ring opening part of an epoxy group was heated and stirred at 100 degreeC. The reaction was carried out to obtain a photosensitive carboxyl group-containing resin solution (B-1).

The resin solution (B-1) thus obtained had a weight average molecular weight (Mw) of 15,000, a solid content of 57%, and an acid value of solids of 79.8 mgKOH / g.

In addition, the weight average molecular weight of obtained resin was the pump LC-6AD by the Shimadzu Corporation Corporation, and the column (Shodex (trademark) KF-804, KF-803, KF-802) by Showa Denko Co., Ltd.). It was measured by high performance liquid chromatography of three connected.

(Synthesis Example 2)

200 parts of methyl methacrylate, 142 parts of glycidyl methacrylate, and 300 parts of diethylene glycol monoethyl ether acetate were added to a three neck flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and azobisisobutyro was used as a catalyst. Nitrile was added and reacted at 80 degreeC for 10 hours, stirring.

Then, 88 parts of methacrylic acid, 2.0 parts of triphenylphosphine and 0.2 part of hydroquinone were added as a stabilizer, added dropwise with a dropping funnel, and reacted at 80 ° C for 16 hours. Furthermore, 140 parts of tetrahydrophthalic anhydride were added, and it reacted at 80 degreeC for 5 hours, and obtained the photosensitive carboxyl group-containing resin solution (B-2).

Thus, the solid content of the resin solution (B-2) obtained was 65%, and the acid value of solid content was 91 mgKOH / g.

(Synthesis Example 3)

1,245 g of polycaprolactonediol (PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol in a 5-liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, and a dihydrate having a carboxyl group 201 g of dimethylolpropionic acid as a hydroxyl compound, 777 g of isophorone diisocyanate as a polyisocyanate and 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and also p-methoxyphenol and di-t 0.5 g of each of -butyl-hydroxytoluene was added thereto.

It stirred by heating to 60 degreeC, stirring, and 0.8 g of dibutyltin dilaurates were added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again, and the stirring is continued at 80 ° C. The infrared absorption spectrum confirms that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group is lost, and the reaction is terminated. The urethane acrylate compound was obtained. It adjusted to non volatile matter = 50 mass% using carbitol acetate, and obtained the photosensitive carboxyl group-containing resin solution (B-3).

Thus, the solid content of the resin solution (B-3) obtained was 50%, and the acid value of solid content was 47 mgKOH / g.

(Synthesis Example 4)

To 600 g of diethylene glycol monoethyl ether acetate orthocresol novolak type epoxy resin (Epiclon N-695 by DIC Corporation, softening point 95 degreeC, epoxy equivalent 214, average functional group number 7.6) 1070 g (glycidyl group number (direction Total number of rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid and 1.5 g of hydroquinone were added thereto, and the resulting mixture was dissolved by heating and stirring to 100 ° C.

Then, 4.3 g of triphenylphosphine was added, and the mixture was heated to 110 ° C and reacted for 2 hours, then heated to 120 ° C and further reacted for 12 hours. 415 g of aromatic hydrocarbon (Solvso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours, it cooled, and the photosensitive carboxyl group-containing resin solution (B-4) )

Thus, the solid content of the resin solution (B-4) obtained was 65%, and the acid value of solid content was 89 mgKOH / g.

(Synthesis Example 5)

To 700 g of diethylene glycol monoethyl ether acetate orthocresol novolak type epoxy resin (Epiclon-695 by DIC Corporation, softening point 95 degreeC, epoxy equivalent 214, average functional group number 7.6) 1070 g (glycidyl group number (aromatic ring) Total number): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly.

Subsequently, 4.3 g of triphenylphosphines were added, and it heated at 110 degreeC, and after reaction for 2 hours, 1.6 g of triphenylphosphines were further added, it heated up at 120 degreeC, and also reacted for 12 hours. 562 g of aromatic hydrocarbons (Solvso 150 manufactured by Exxon Chemical Co., Ltd.) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were added to the reaction solution, and the reaction was carried out at 110 ° C for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylates were thrown into the obtained reaction liquid, and it reacted at 115 degreeC for 4 hours, and obtained the photosensitive carboxyl group-containing resin solution (B-5).

Thus, the solid content of the resin solution (B-5) obtained was 65%, and the acid value of solid content was 87 mgKOH / g.

(Synthesis Example 6)

925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide were dissolved in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 DEG C and then 81.2 parts of 98.5% NaOH was added thereto at 70 DEG C over 100 minutes while stirring. After addition, reaction was further performed at 70 degreeC for 3 hours.

Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further, 30% NaOH 10 Part was added and reacted at 70 ° C for 1 hour. After completion of the reaction, water washing was performed twice with 200 parts of water. Methyl isobutyl ketone was distilled off from the oil layer after oil-water separation, and 370 parts of epoxy resins (a-1) of epoxy equivalent 290 and softening point 62 degreeC were obtained.

2900 parts (10 equivalents) of obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate were thrown in, and it heated and stirred at 90 degreeC, and dissolved the reaction mixture. Subsequently, the reaction solution was cooled to 60 ° C, 16.7 parts of triphenylphosphine was added, heated to 100 ° C, and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were put into this, it heated at 95 degreeC, and it reacted for about 6 hours, and obtained the photosensitive carboxyl group-containing resin solution (B-6).

Thus, the solid content of the resin solution (B-6) obtained was 65%, and the acid value of solid content was 100 mgKOH / g.

(Synthesis Example 7)

119.4 g of novolak-type cresol resin (Showa Chemical Co., Ltd., Shool C RG951, OH equivalents: 119.4) in an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 1.19 g of potassium hydroxide, and 19.4 g was added, the inside of the system was purged with nitrogen while stirring, and the temperature was increased by heating.

Next, 63.8 g of propylene oxide was slowly added dropwise and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the mixture was cooled to room temperature, 1.56 g of 89% phosphoric acid was added to the reaction solution, mixed to neutralize potassium hydroxide, and propylene oxide of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. The reaction solution was obtained. This was an average of 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group.

293.0 g of the alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was supplied. Blown at a rate of 10 ml / min, and reacted at 110 degreeC for 12 hours, stirring. The water produced by the reaction flowed out of 12.6 g of an azeotropic mixture with toluene.

Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of an aqueous 15% sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate to obtain a novolak-type acrylate resin solution.

Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blown tube, and the air was blown at a rate of 10 ml / min and stirred. 60.8 g of tetrahydrophthalic anhydride was added gradually, it was made to react at 95-101 degreeC for 6 hours, and the photosensitive carboxyl group-containing resin solution (B-7) was obtained.

Thus, the solid content of the resin solution (B-7) obtained was 71%, and the acid value of solid content was 88 mgKOH / g.

In addition, ZCR-1601H (an acid value from Nippon Kayaku Co., Ltd .: 96 mgKOH / g, solid content: 65%) which is a commercial item was used as resin solution B-8 as it was.

Using these resin solutions B-1-B-8, it mix | blends with the compounding (mass part) shown in Table 1, pre-mixes with a stirrer, and knead | mixes with a triaxial roll mill, Examples 1-8 and Comparative Example 1 And 2, the photocurable resin composition for soldering resists was manufactured.

In addition, when the dispersion degree of the photocurable resin composition obtained here was evaluated by the particle size measurement by the grinder made by Eriksen, it was 15 micrometers or less, respectively.

* 1: A-1

* 2: A-2

(CGI-325 made by BASF Japan company)

* 3: A-3 2methyl-1- (4-methylthiophenyl) -2morpholinopropane-1one

* 4: A-4 2,4-diethyl thioxanthone

Common Ingredients:

Ethylenic unsaturated group containing compound: 20 parts of dipentaerythritol hexaacrylate (DPHA by Nippon Kayaku Co., Ltd.)

Thermosetting resin: 15 parts of phenol novolac type epoxy resin

Pigment: C.I. Pigment Blue 15: 3 0.3

      C.I. Pigment Yellow 147 0.8

Thermosetting Catalysts: Melamine Part 5

Chain transfer agent and adhesion imparting agent: 0.5 parts of mercaptobenzothiazole

Thixotropic imparting agent: 6 parts of hydrotalcite (manufactured by Kyowa Chemical Co., Ltd.)

3 parts of silicone antifoam

Organic solvent: 5 parts of DPM (dipropylene glycol monomethyl ether)

Filling material: 100 parts of barium sulfate (barium sulfate B30 manufactured by Sakai Chemical Industries, Ltd.)

[Performance evaluation]

<Optimum exposure dose>

The circuit pattern board | substrate of copper thickness 35 micrometers was rinsed and rinsed after buff roll polishing, and the photocurable resin composition of an Example and a comparative example was apply | coated to the whole surface by the screen printing method. This was dried for 60 minutes in a hot air circulation drying furnace at 80 ° C.

This board is a high pressure mercury lamp mounted exposure apparatus (mercury short arc lamp mounted exposure machine manufactured by Oak Seisakusho Co., Ltd.), a high pressure mercury lamp direct drawing exposure apparatus (super high pressure mercury lamp lamp direct drawing exposure machine manufactured by Dainippon Screen Corporation (Marculex; registered trademark)) And a direct drawing apparatus (405 nm laser exposure apparatus manufactured by Hitachi Beer Mechanics Co., Ltd.), and exposed through a step tablet (Kodak No2), respectively. Moreover, this board | substrate was developed for 60 second on condition of temperature: 30 degreeC, spray pressure: 0.2 MPa, and developing solution: 1 mass% sodium carbonate aqueous solution, and made the optimum exposure amount when the pattern of the remaining step tablet is seven steps.

<Maximum developing life>

The photocurable resin composition of each Example and the comparative example was apply | coated whole surface by the screen printing on the patterned copper foil board | substrate, dried at 80 degreeC, the board | substrate was taken out every 10 minutes from 20 minutes to 80 minutes, and it cooled to room temperature. .

This board | substrate was developed for 60 second on condition of the temperature of 30 degreeC, spray pressure: 0.2 Mpa, and developing solution: 1 mass% sodium carbonate aqueous solution, and the maximum allowable drying time which a residue does not remain was made into the maximum developing life.

[Characteristic evaluation]

The photocurable resin composition of each Example and the comparative example was apply | coated whole surface by screen printing on the patterned copper foil board | substrate, and it cooled to room temperature. The soldering resist pattern was exposed by the optimal exposure amount using the exposure apparatus which mounted the mercury short arc lamp on this board | substrate.

And this board | substrate was developed for 60 second on condition of the temperature of 30 degreeC, spray pressure: 0.2 Mpa, and developing solution: 1 mass% sodium carbonate aqueous solution, and the resist pattern was obtained. Further, the substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 using a UV conveyor, and then heated at 150 ° C. for 60 minutes to cure.

The properties of the obtained printed board (evaluation board) were evaluated as follows.

&Lt; Soldering heat resistance &

The evaluation board | substrate with which the rosin type flux was apply | coated was immersed in the solder tank previously set to 260 degreeC, and the flux was wash | cleaned with denatured alcohol, and it evaluated about swelling and peeling of the resist layer by visual observation. The criteria are as follows.

(Circle): Peeling is not seen even if it repeats immersion 3 times or more for 10 second.

(Triangle | delta): It peels a little when repeating immersion 3 times or more for 10 second.

X: swelled in a resist layer within 3 times of immersion for 10 second, and there exists peeling

Electroless Gold Plating Resistant

Plating was performed under conditions of 0.5 μm nickel and 0.03 μm gold using an electroless nickel plating bath and an electroless gold plating bath, which are commercially available products. Evaluated. The criteria are as follows.

◎: no seepage and peeling

(Circle): Slightly penetrated after plating, but does not peel off after tape peeling.

(Triangle | delta): Very slight seepage after plating, peeling is also seen after tape peeling.

X: peeling after plating

<Electric Insulation Characteristics>

The comb-shaped electrode B coupon of IPCB-25 was used for the copper foil substrate. A bias voltage of DC 100V was applied to this comb-shaped electrode, and the presence or absence of the migration after 1,000 hours was confirmed by 85 degreeC and the constant temperature / humidity tank of 85% R.H. The criteria are as follows.

◎: no change at all

○: extremely slightly changed

△: discoloration is seen

×: The migration is occurring

These evaluation results are shown in Table 2.

[Dry Film Evaluation]

The photocurable resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were diluted with methyl ethyl ketone, coated on a PET film, and dried at 80 ° C. for 30 minutes to form a resin composition layer having a thickness of 20 μm. Moreover, the cover film was bonded together on it, the dry film was produced, and it was set as Example 9, 10 and Comparative Examples 3 and 4, respectively. And the cover film was peeled off, the film was heat-laminated to the patterned copper foil board | substrate, and the resin composition layer was stuck on the copper foil board | substrate.

The substrate thus obtained was exposed in the same manner as the substrate formed by applying the photocurable resin composition. In addition, the high pressure mercury lamp mounting exposure apparatus (mercury shot arc lamp mounting exposure machine made by Oak Seisakusho Co., Ltd.), and the direct drawing apparatus (355 nm laser exposure apparatus Orbotech Co., Ltd. product Paragon 8000) were used.

And after peeling a carrier film, this board | substrate was developed for 60 second on condition of temperature: 30 degreeC, spray pressure: 0.2MPa, developing solution: 1 mass% sodium carbonate aqueous solution, and the resist pattern was obtained. Moreover, after heat-hardening for 60 minutes with the 150 degreeC hot air dryer, ultraviolet irradiation was similarly performed and the test board | substrate for dry film evaluation was produced.

About the obtained test board | substrate, the evaluation test of each characteristic was similarly performed.

The evaluation results are shown in Table 3.

Thus, by using the photocurable resin composition of this embodiment and its dry film, it is highly sensitive and short-time exposure is possible, and it does not deteriorate developability, and it is favorable solder heat resistance, electroless plating resistance, electrical insulation characteristics, etc. It can be seen that the reliability of can be obtained. And by using such a photocurable resin composition, even when using the exposure apparatus which has high alignment accuracy, such as direct exposure, it becomes possible to obtain high productivity.

[Out gas amount evaluation]

Using resin solution B-1, it mix | blended by the compounding (mass part) shown in Table 4, and carried out similarly to manufacture the photocurable resin composition for soldering resists of Examples 11 and 12 and Comparative Examples 5 and 6. In addition, A-1 is a photoinitiator used in Examples 1-8.

* 5: A-5

* 6: A-6

1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (IRG-OXE01 by BASF Japan)

* 7: A-7 (IRG907 by BASF Japan company)

* 8: trimethylolpropanetriacrylate

* 9: Bisphenol A diglycidyl ether (made by Mitsubishi Chemical Corporation)

* 10: polymerization inhibitor phenothiazine

After apply | coating these photocurable resin compositions on a glass substrate by screen printing, and drying at 80 degreeC for 30 minute (s) using a hot air circulation type drying furnace, it exposed at the appropriate exposure amount using the high pressure mercury lamp exposure apparatus by Oak Seisakusho Co., Ltd. .

And a part of the coating film was scraped off as it is, and it was set as the sample before thermosetting, and the remainder was hardened at 150 degreeC for 60 minutes, and the coating film was scraped off and it was set as the sample after thermosetting.

1 mg of each sample was heated by purging & trapping for 5 minutes at 150 ° C for 5 minutes and at 150 ° C for 30 minutes, after thermosetting for 5 minutes at 245 ° C. Quantification

Table 5 shows the appropriate exposure dose and the quantitative results of the volatile components (out gas) derived from the generated photopolymerization initiator.

11 less than 0.1%

Thus, in the photocurable resin composition of this embodiment, while having high sensitivity, the amount of volatile components (out gas) derived from a photoinitiator can be suppressed also in the sample before thermosetting and the sample after thermosetting. It can be seen that. Therefore, it becomes possible to suppress contamination at the time of exposure by direct exposure etc. or at the time of mounting by reflow in a subsequent process.

Claims (7)

A photopolymerization initiator having two oxime ester groups in a molecule represented by the following formula (I),
Carboxyl group-containing resin,
A compound having two or more ethylenically unsaturated groups in a molecule, and
A thermosetting resin is included, The photocurable resin composition characterized by the above-mentioned.
(I)

(In formula, R <_1> is a hydrogen atom, a C1-C17 alkyl group, a C1-C8 alkoxy group, a phenyl group, a phenyl group (C1-C17 alkyl group, a C1-C8 alkoxy group, an amino group, C1-C8). Substituted by an alkylamino or dialkylamino group having an alkyl group of 1), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Substituted with an amino group), and R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms and carbon atoms). Substituted by an alkylamino group or dialkylamino group having 1 to 8 alkoxy groups, amino groups, alkyl groups having 1 to 8 carbon atoms, and naphthyl groups (alkyl groups having 1 to 17 carbon atoms, 1 carbon atom). And an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, n represents an integer from 0 to 1) It is obtained by apply | coating and drying the photocurable resin composition of Claim 1 on a film, The dry film characterized by the above-mentioned. The dry coating film obtained by apply | coating and drying the photocurable resin composition of Claim 1 to a base material, or the dry film obtained by apply | coating and drying the said photocurable resin composition on a film to a base material is obtained by irradiation of an active energy ray. Hardened | cured material obtained by making it photocure. The dry coating film obtained by apply | coating and drying the photocurable resin composition of Claim 1 to a base material, or the dry film obtained by apply | coating and drying the said photocurable resin composition on a film to a base material is obtained by irradiation of an active energy ray. It has a pattern of the hardened | cured material obtained by photocuring by the printed wiring board. delete delete delete